Polytriazine derivatives containing polyalkylpiperidinyloxy or polyalkylpiperidinylamino groups

ABSTRACT

Compounds of the formula (I) ##STR1## wherein n is a number from 1 to 20; 
     the radicals R 1  are independently of one another hydrogen, C 1  -C 8  alkyl, --O, --OH, --CH 2  CN, C 1  -C 18  alkoxy, C 5  -C 12  cycloalkoxy, C 3  -C 6  alkenyl, C 7  -C 9  phenylalkyl which is unsubstituted or substituted on the phenyl by 1, 2 or 3 C 1  -C 4  alkyl; or C 1  -C 8  acyl; 
     R 2  has one of the meanings given for R 1  ; 
     X is C 2  -C 10  alkylene; and 
     Y is --O-- or &gt;NH; 
     with the proviso that in the individual recurrent units of the formula (I), each of the radicals R 1 , R 2 , X and Y has the same or different definitions; 
     are very effective as light stabilizers, heat stabilizers and oxidation stabilizers for organic materials, in particular synthetic polymers.

The present invention relates to polytriazine derivatives containingpolyalkylpiperidinyloxy or polyalkylpiperidinylamino groups, to the usethereof for stabilizing organic materials, in particular syntheticpolymers, against degradation induced by light, heat or oxidation and tothe organic materials thus stabilized.

The use of polytriazine derivatives containing polyalkylpiperidinylgroups as stabilizers for organic materials is for example described inUS-A-4 086 204, US-A-4 108 829, US-A-4 331 586, US-A-4 335 242, US-A-4816 507, US-A-4 997 938, EP-A-357 223, EP-A-479 724, EP-A-601 978 andEP-A-659 750.

In US-A-4 442 250, the use of macrocyclic triazine compounds containingpolyalkylpiperidinyl groups and the stabilizing activity therof isdisclosed.

The present invention relates to a compound of the formula (I) ##STR2##wherein n is a number from 1 to 20;

the radicals R₁ are independently of one another hydrogen, C₁ -C₈ alkyl,--O, --OH, --CH₂ CN, C₁ -C₁₈ alkoxy, C₅ -C₁₂ cycloalkoxy, C₃ -C₆alkenyl, C₇ -C₉ phenylalkyl which is unsubstituted or substituted on thephenyl by 1, 2 or 3 C₁ -C₄ alkyl; or C₁ -C₈ acyl;

R₂ has one of the meanings given for R₁ ;

X is C₂ -C₁₀ alkylene; and

Y is --O-- or >NH;

with the proviso that in the individual recurrent units of the formula(I), each of the radicals R₁, R₂, X and Y has the same or differentdefinitions.

Examples of alkyl containing not more than 8 carbon atoms are methyl,ethyl, propyl, isopropyl, butyl, 2-butyl, isobutyl, t-butyl, pentyl,2-pentyl, hexyl, heptyl and octyl. One of the preferred meanings of R₁and R₂ is C₁ -C₄ alkyl, in particular methyl.

Examples of alkoxy containing not more than 18 carbon atoms are methoxy,ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, pentoxy, isopentoxy,hexoxy, heptoxy, octoxy, decyloxy, dodecyloxy, tetradecyloxy,hexadecyloxy and octadecyloxy. C₆ -C₁₂ Alkoxy, in particular heptoxy andoctoxy, is preferred.

Examples of C₅ -C₁₂ cycloalkoxy are cyclopentoxy, cyclohexoxy,cycloheptoxy, cyclooctoxy, cyclodecyloxy and cyclododecyloxy. C₅ -C₈Cycloalkoxy, in particular cyclopentoxy and cyclohexoxy, is preferred.

Examples of C₃ -C₆ alkenyl are allyl, 2-methylallyl, butenyl andhexenyl. Alkenyls in which the carbon atom in the 1-position issaturated are preferred, and allyl is particularly preferred.

Examples of C₇ -C₉ phenylalkyl which is unsubstituted or substituted onthe phenyl by 1, 2 or 3 C₁ -C₄ alkyl are benzyl, methylbenzyl,dimethylbenzyl, trimethylbenzyl, t-butylbenzyl and 2-phenylethyl. Benzylis preferred.

Examples of C₁ -C₈ acyl are formyl, acetyl, propionyl, butyryl,pentanoyl, hexanoyl, heptanoyl, octanoyl and benzoyl. C₁ -C₈ Alkanoyland benzoyl are preferred. Acetyl is especially preferred.

Examples of C₂ -C₁₀ alkylene are ethylene, propylene, trimethylene,2-methyltrimethylene, 2,2-dimethyltrimethylene, tetramethylene,pentamethylene, hexamethylene, trimethylhexamethylene, octamethylene anddecamethylene. X is preferably C₂ -C₆ alkylene, in particular hexylene.

The variable n may be for example a number from 2 to 20 or 3 to 20.

In the individual recurrent structural units of the formula (I), each ofthe radicals R₁, R₂, X and Y has preferably the same definition.

The radicals R₁ are preferably identical.

Preferred compounds of the formula (I) are those wherein the radicals R₁are independently of one another hydrogen, C₁ -C₄ alkyl, --OH, C₆ -C₁₂alkoxy, C₅ -C₈ cycloalkoxy, allyl, benzyl or acetyl, in particularhydrogen or C₁ -C₄ alkyl; and R₂ has one of the meanings given for R₁.

Particularly preferred compounds of the formula (I) are those whereinthe radicals R₁ are identical and are hydrogen, methyl or cyclohexyloxy;R₂ has one of the meanings given for R₁ ; and X is C₂ -C₆ alkylene; withthe proviso that in the individual recurrent units of the formula (I),each of the radicals R₁, R₂, X and Y has the same definitions.

Compounds of the formula (I) of special interest are those wherein theradicals R₁ are identical and are hydrogen or methyl; and R₂ has one ofthe meanings given for R₁.

Y is preferably --O--.

The compounds of the formula (I) may be prepared for example in analogyto the method described in US-A-4 086 204 by reacting a compound of theformula (II) ##STR3## with a compound of the formula (III) ##STR4##wherein R₁, R₂, X and Y have the meanings given above in an appropriatemolar ratio, in particular a stoichiometric ratio.

The reaction is preferably carried out in an inert organic solvent suchas dioxane, toluene, xylene, trimethylbenzene, t-amyl alcohol, 1,2-dichloroethane or mixtures of the aforementioned solvents at atemperature of e.g. 20° C. to 180° C. A temperature of 60° C. to 150° C.is preferred. Furthermore, the reaction is conveniently carried out inthe presence of an organic or inorganic base such as triethylamine,triisopropylamine, tributylamine, sodium hydroxide, sodium carbonate,potassium hydroxide or potassium carbonate.

The compounds of the formula (II) can be obtained, for example, directlyfrom cyanuric chloride and the appropriate 4-hydroxypiperidinederivative or 4-aminopiperidine derivative in an inert organic solventsuch as toluene, xylene or trimethylbenzene in the presence ofisopropanol, isobutanol or isoamylalcohol at a molar ratio with regardto the 4-hydroxypiperidine derivative or 4-aminopiperidine derivative ofe.g. 1.3:1 to 1:1. Isopropanol and the molar ratio of 1.2:1 arepreferred.

The reaction is conveniently carried out at a temperature of 0° C. to60° C., in particular 30° C. to 60° C.

The compounds of the formula (II) wherein Y is --O-- can also beobtained, for example, from cyanuric chloride and a compound of theformula (IV) ##STR5## wherein R₂ has the meanings given above and M isan alkaline metal such as lithium, sodium or potassium, at theappropriate molar ratio in an inert organic solvent such as toluene,xylene or trimethylbenzene at a temperature of -20° C. to 70° C.,preferably 0° C. to 60° C.

A further example for the preparation of the compounds of the formula(I) is the reaction of cyanuric chloride with a compound of the formula(III) in the appropriate molar ratio, preferably in the stoichiometricratio, to obtain a compound of the formula (V) ##STR6## wherein n, R₁and X have the definitions given above. The polytriazine of the formula(V) is conveniently reacted with the appropriate 4-aminopiperidinederivative or with a compound of the formula (VI) ##STR7## wherein R₂has the meanings given above and L is hydrogen or an alkaline metal suchas lithium , sodium or potassium.

The reaction is preferably carried out in an inert organic solvent, forexample toluene, xylene or trimethylbenzene. When L is hydrogen, thereaction is conveniently carried out in the presence of a base, inparticular an inorganic base such as sodium or potassium hydroxide orcarbonate. The reaction temperature is for example 60° C. to 180° C.,preferably 100° C. to 180° C.

The compounds of the formula (IV) and (VI) wherein M and L are analkaline metal may be obtained, for example, by treating the appropriate4-hydroxypiperidine derivative with an alkaline alcoholate or analkaline metal in an inert organic solvent such as toluene, xylene ortrimethylbenzene at reflux temperature, simultaneously distilling offthe alcohol formed during the reaction.

The starting materials used in the above preparations are known and canbe prepared according to known methods, if not commercially available

During the preparation of the compounds of the formula (I), amacrocyclic compound of the fomula ##STR8## wherein R₁, R₂, X and Y areas defined above may be formed as a by-product in an amount of e.g. upto 20%. This by-product can be separated from the reaction mixture byusual methods such as e.g. filtration and so on.

The indicated by-product is also useful as light stabilizer, heatstabilizer and oxidation stabilizer for organic materials.

The compounds of the formula (I) are very effective in improving thelight, heat and oxidation resistance of organic materials, especiallysynthetic polymers and copolymers.

Examples of organic materials which can be stabilized are:

1. Polymers of monoolefins and diolefins, for example polypropylene,polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene, polyisoprene orpolybutadiene, as well as polymers of cycloolefins, for instance ofcyclopentene or norbornene, polyethylene (which optionally can becrosslinked), for example high density polyethylene (HDPE), high densityand high molecular weight polyethylene (HDPE-HMW), high density andultrahigh molecular weight polyethylene (HDPE-UHMW), medium densitypolyethylene (MDPE), low density polyethylene (LDPE), linear low densitypolyethylene (LLDPE), branched low density polyethylene (BLDPE).

Polyolefins, i.e. the polymers of monoolefins exemplified in thepreceding paragraph, preferably polyethylene and polypropylene, can beprepared by different, and especially by the following, methods:

a) radical polymerisation (normally under high pressure and at elevatedtemperature).

b) catalytic polymerisation using a catalyst that normally contains oneor more than one metal of groups IVb, Vb, VIb or VII of the PeriodicTable. These metals usually have one or more than one ligand, typicallyoxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenylsand/or aryls that may be either π- or σ-coordinated. These metalcomplexes may be in the free form or fixed on substrates, typically onactivated magnesium chloride, titanium(III) chloride, alumina or siliconoxide. These catalysts may be soluble or insoluble in the polymerisationmedium. The catalysts can be used by themselves in the polymerisation orfurther activators may be used, typically metal alkyls, metal hydrides,metal alkyl halides, metal alkyl oxides or metal alkyloxanes, saidmetals being elements of groups Ia, IIa and/or IIIa of the PeriodicTable. The activators may be modified conveniently with further ester,ether, amine or silyl ether groups. These catalyst systems are usuallytermed Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont),metallocene or single site catalysts (SSC).

2. Mixtures of the polymers mentioned under 1), for example mixtures ofpolypropylene with polyisobutylene, polypropylene with polyethylene (forexample PP/HDPE, PP/LDPE) and mixtures of different types ofpolyethylene (for example LDPE/HDPE).

3. Copolymers of monoolefins and diolefins with each other or with othervinyl monomers, for example ethylene/propylene copolymers, linear lowdensity polyethylene (LLDPE) and mixtures thereof with low densitypolyethylene (LDPE), propylene/but-1-ene copolymers,propylene/isobutylene copolymers, ethylene/but-1 -ene copolymers,ethylene/hexene copolymers, ethylene/methylpentene copolymers,ethylene/heptene copolymers, ethylene/octene copolymers,propylene/butadiene copolymers, isobutylene/isoprene copolymers,ethylene/alkyl acrylate copolymers, ethylene/alkyl methacrylatecopolymers, ethylene/vinyl acetate copolymers and their copolymers withcarbon monoxide or ethylene/acrylic acid copolymers and their salts(ionomers) as well as terpolymers of ethylene with propylene and a dienesuch as hexadiene, dicyclopentadiene or ethylidene-norbornene; andmixtures of such copolymers with one another and with polymers mentionedin 1) above, for example polypropylene/ethylene-propylene copolymers,LDPE/ethylene-vinyl acetate copolymers (EVA), LDPE/ethylene-acrylic acidcopolymers (EAA), LLDPE/EVA, LLDPE/EAA and alternating or randompolyalkylene/carbon monoxide copolymers and mixtures thereof with otherpolymers, for example polyamides.

4. Hydrocarbon resins (for example C₅ -C₉) including hydrogenatedmodifications thereof (e.g. tackifiers) and mixtures of polyalkylenesand starch.

5. Polystyrene, poly(p-methylstyrene), poly(α-methylstyrene).

6. Copolymers of styrene or α-methylstyrene with dienes or acrylicderivatives, for example styrene/butadiene, styrene/acrylonitrile,styrene/alkyl methacrylate, styrene/butadiene/alkyl acrylate,styrene/butadiene/alkyl methacrylate, styrene/maleic anhydride,styrene/acrylonitrile/methyl acrylate; mixtures of high impact strengthof styrene copolymers and another polymer, for example a polyacrylate, adiene polymer or an ethylene/propylene/diene terpolymer; and blockcopolymers of styrene such as styrene/butadiene/styrene,styrene/isoprene/styrene, styrene/ethylene/butylene/styrene orstyrene/ethylene/propylene/styrene.

7. Graft copolymers of styrene or (α-methylstyrene, for example styreneon polybutadiene, styrene on polybutadiene-styrene orpolybutadiene-acrylonitrile copolymers; styrene and acrylonitrile (ormethacrylonitrile) on polybutadiene; styrene, acrylonitrile and methylmethacrylate on polybutadiene; styrene and maleic anhydride onpolybutadiene; styrene, acrylonitrile and maleic anhydride or maleimideon polybutadiene; styrene and maleimide on polybutadiene; styrene andalkyl acrylates or methacrylates on polybutadiene; styrene andacrylonitrile on ethylene/propylene/diene terpolymers; styrene andacrylonitrile on polyalkyl acrylates or polyalkyl methacrylates, styreneand acrylonitrile on acrylate/butadiene copolymers, as well as mixturesthereof with the copolymers listed under 6), for example the copolymermixtures known as ABS, MBS, ASA or AES polymers.

8. Halogen-containing polymers such as polychloroprene, chlorinatedrubbers, chlorinated and brominated copolymer of isobutylene-isoprene(halobutyl rubber), chlorinated or sulfochlorinated polyethylene,copolymers of ethylene and chlorinated ethylene, epichlorohydrin homo-and copolymers, especially polymers of halogen-containing vinylcompounds, for example polyvinyl chloride, polyvinylidene chloride,polyvinyl fluoride, polyvinylidene fluoride, as well as copolymersthereof such as vinyl chloride/vinylidene chloride, vinyl chloride/vinylacetate or vinylidene chloride/vinyl acetate copolymers.

9. Polymers derived from α,β-unsaturated acids and derivatives thereofsuch as polyacrylates and polymethacrylates; polymethyl methacrylates,polyacrylamides and polyacrylonitriles, impact-modified with butylacrylate.

10. Copolymers of the monomers mentioned under 9) with each other orwith other unsaturated monomers, for example acrylonitrile/butadienecopolymers, acrylonitrile/alkyl acrylate copolymers,acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl halidecopolymers or acrylonitrile/alkyl methacrylate/butadiene terpolymers.

11. Polymers derived from unsaturated alcohols and amines or the acylderivatives or acetals thereof, for example polyvinyl alcohol, polyvinylacetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate,polyvinyl butyral, polyallyl phthalate or polyallyl melamine; as well astheir copolymers with olefins mentioned in 1) above.

12. Homopolymers and copolymers of cyclic ethers such as polyalkyleneglycols, polyethylene oxide, polypropylene oxide or copolymers thereofwith bisglycidyl ethers.

13. Polyacetals such as polyoxymethylene and those polyoxymethyleneswhich contain ethylene oxide as a comonomer; polyacetals modified withthermoplastic polyurethanes, acrylates or MBS.

14. Polyphenylene oxides and sulfides, and mixtures of polyphenyleneoxides with styrene polymers or polyamides.

15. Polyurethanes derived from hydroxyl-terminated polyethers,polyesters or polybutadienes on the one hand and aliphatic or aromaticpolyisocyanates on the other, as well as precursors thereof.

16. Polyamides and copolyamides derived from diamines and dicarboxylicacids and/or from aminocarboxylic acids or the corresponding lactams,for example polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12,4/6, 12/12, polyamide 11, polyamide 12, aromatic polyamides startingfrom m-xylene diamine and adipic acid; polyamides prepared fromhexamethylenediamine and isophthalic or/and terephthalic acid and withor without an elastomer as modifier, for examplepoly-2,4,4,-trimethylhexamethylene terephthalamide or poly-m-phenyleneisophthalamide; and also block copolymers of the aforementionedpolyamides with polyolefins, olefin copolymers, ionomers or chemicallybonded or grafted elastomers; or with polyethers, e.g. with polyethyleneglycol, polypropylene glycol or poly tetramethylene glycol; as well aspolyamides or copolyamides modified with EPDM or ABS; and polyamidescondensed during processing (RIM polyamide systems).

17. Polyureas, polyimides, polyamide-imides, polyetherimids,polyesterimids, polyhydantoins and polybenzimidazoles.

18. Polyesters derived from dicarboxylic acids and diols and/or fromhydroxycarboxylic acids or the corresponding lactones, for examplepolyethylene terephthalate, polybutylene terephthalate,poly-1,4-dimethylolcyclohexane terephthalate and polyhydroxybenzoates,as well as block copolyether esters derived from hydroxyl-terminatedpolyethers; and also polyesters modified with polycarbonates or MBS.

19. Polycarbonates and polyester carbonates.

20. Polysulfones, polyether sulfones and polyether ketones.

21. Crosslinked polymers derived from aldehydes on the one hand andphenols, ureas and melamines on the other hand, such asphenol/formaldehyde resins, urea/formaldehyde resins andmelamine/formaldehyde resins.

22. Drying and non-drying alkyd resins.

23. Unsaturated polyester resins derived from copolyesters of saturatedand unsaturated dicarboxylic acids with polyhydric alcohols and vinylcompounds as crosslinking agents, and also halogen-containingmodifications thereof of low flammability.

24. Crosslinkable acrylic resins derived from substituted acrylates, forexample epoxy acrylates, urethane acrylates or polyester acrylates.

25. Alkyd resins, polyester resins and acrylate resins crosslinked withmelamine resins, urea resins, isocyanates, isocyanurates,polyisocyanates or epoxy resins.

26. Crosslinked epoxy resins derived from aliphatic, cycloaliphatic,heterocyclic or aromatic glycidyl compounds, e.g. products of diglycidylethers of bisphenol A and bisphenolF, which are crosslinked withcustomary hardeners such as anhydrides or amines, with or withoutaccelerators.

27. Natural polymers such as cellulose, rubber, gelatin and chemicallymodified homologous derivatives thereof, for example cellulose acetates,cellulose propionates and cellulose butyrates, or the cellulose etherssuch as methyl cellulose; as well as rosins and their derivatives.

28. Blends of the aforementioned polymers (polyblends), for examplePP/EPDM, Polyamide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS,PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic PUR,PC/thermoplastic PUR, POM/acrylate, POM/WMBS, PPO/HIPS, PPO/PA 6.6 andcopolymers, PA/HDPE, PA/PP, PA/PPO, PBT/PC/ABS or PBT/PET/PC.

29. Naturally occurring and synthetic organic materials which are puremonomeric compounds or mixtures of such compounds, for example mineraloils, animal and vegetable fats, oil and waxes, or oils, fats and waxesbased on synthetic esters (e.g. phthalates, adipates, phosphates ortrimellitates) and also mixtures of synthetic esters with mineral oilsin any weight ratios, typically those used as spinning compositions, aswell as aqueous emulsions of such materials.

30. Aqueous emulsions of natural or synthetic rubber, e.g. natural latexor latices of carboxylated styrene/butadiene copolymers.

The invention thus also relates to a composition comprising an organicmaterial susceptible to oxidative, thermal or light-induced degradationand at least one compound of the formula (I).

The organic material is preferably a synthetic polymer, moreparticularly one selected from the aforementioned groups. Polyolefinsare preferred and polyethylene and polypropylene are particularlypreferred.

A further embodiment of the instant invention is a method forstabilizing an organic material against degradation induced by light,heat or oxidation, which comprises incorporating into said organicmaterial at least one compound of the formula (I).

The compounds of the formula (I) can be used in various proportionsdepending on the nature of the material to be stabilized, on the end useand on the presence of other additives.

In general, it is appropriate to use, for example, 0.01 to 5% by weightof the compounds of the formula (I), relative to the weight of thematerial to be stabilized, preferably 0.05 to 1%.

The compounds of the formula (I) can be added, for example, to thepolymeric materials before, during or after the polymerization orcrosslinking of the said materials. Furthermore, they can beincorporated in the polymeric materials in the pure form or encapsulatedin waxes, oils or polymers.

In general, the compounds of the formula (I) can be incorporated in thepolymeric materials by various processes, such as dry mixing in the formof powder, or wet mixing in the form of solutions or suspensions or alsoin the form of a masterbatch; in such operations, the polymer can beused in the form of powder, granules, solutions, suspensions or in theform of latices.

The materials stabilized with the compounds of the formula (I) can beused for the production of mouldings, films, tapes, monofilaments,fibres, surface coatings and the like.

If desired, other conventional additives for synthetic polymers, such asantioxidants, UV absorbers, nickel stabilizers, pigments, fillers,plasticizers, corrosion inhibitors and metal deactivators, can be addedto the organic materials containing the compounds of the formula (I).

Particular examples of said conventional additives are:

1. Antioxidants

1.1. Alkylated monophenols, for example2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol,2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol,2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol,2-(α-methylcyclohexyl)-4,6-di-methylphenol,2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol,2,6-di-tert-butyl-4-methoxymethylphenol, nonylphenols which are linearor branched in the side chains, for example,2,6-di-nonyl-4-methylphenol,2,4-dimethyl-6-(1'-methylundec-1'-yl)phenol,2,4-dimethyl-6-(1'-methylheptadec-1'-yl)phenol,2,4-dimethyl-6-(1'-methyltridec-1'-yl)phenol and mixtures thereof.

1.2. Alkylthiomethylphenols, for example2,4-dioctylthiomethyl-6-tert-butylphenol,2,4-di-octylthiomethyl-6-methylphenol,2,4-dioctylthiomethyl-6-ethylphenol, 2,6-di-dodecylthio-methyl-4-nonylphenol.

1.3. Hydroquinones and alkylated hydroquinones, for example2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone,2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octa-decyloxyphenol,2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole,3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenylstearate, bis-(3,5-di-tert-butyl-4-hydroxyphenyl) adipate.

1.4. Tocopherols, for example α-tocopherol, β-tocopherol, γ-tocopherol,δ-tocopherol and mixtures thereof (Vitamin E).

1.5. Hydroxylated thiodiphenyl ethers, for example2,2'-thiobis(6-tert-butyl-4-methylphenol), 2,2'-thiobis(4-octylphenol),4,4'-thiobis(6-tert-butyl-3-methylphenol), 4,4'-thiobis(6-tert-butyl-2-methylphenol), 4,4'-thiobis-(3,6-di-sec-amylphenol),4,4'-bis-(2,6-dimethyl-4-hydroxyphenyl) disulfide.

1.6. Alkylidenebisphenols, for example2,2'-methylenebis(6-tert-butyl-4-methylphenol),2,2'-methylenebis(6-tert-butyl-4-ethylphenol), 2,2'-methylenebis4-methyl-6-(α-methylcyclohexyl)-phenol!,2,2'-methylenebis(4-methyl-6-cyclohexylphenol),2,2'-methylenebis(6-nonyl-4-methylphenol),2,2'-methylenebis(4,6-di-tert-butylphenol),2,2'-ethylidenebis(4,6-di-tert-butylphenol),2,2'-ethylidenebis(6-tert-butyl-4-isobutylphenol), 2,2'-methylenebis6-(α-methylbenzyl)-4-nonylphenol!, 2,2'-methylenebis6-(α,α-dimethylbenzyl)-4-nonylphenol!,4,4'-methylenebis(2,6-di-tert-butylphenol),4,4'-methylenebis(6-tert-butyl-2-methylphenol), 1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol,1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, 1,1-bis(5-tert-butyl-4-hydroxy-2-methyl-phenyl)-3-n-dodecylmercaptobutane,ethylene glycol bis 3,3-bis(3'-tert-butyl-4'-hydroxyphenyl)butyrate!,bis(3-tert-butyl-4-hydroxy-5-methyl-phenyl)dicyclopentadiene, bis2-(3'-tert-butyl-2'-hydroxy-5'-methylbenzyl)-6-tert-butyl-4-methylphenyl!terephthalate,1,1-bis-(3,5-dimethyl-2-hydroxyphenyl)butane,2,2-bis-(3,5-di-tert-butyl-4-hydroxyphenyl) propane,2,2-bis-(5-tert-butyl-4-hydroxy2-methylphenyl)-4-n-dodecylmercaptobutane,1,1,5,5-tetra-(5-tert-butyl-4-hydroxy2-methylphenyl)pentane.

1.7. O--, N--and S--benzyl compounds, for example3,5,3',5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether,octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate,tridecyl-4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetate,tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine,bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate,bis(3,5-di-tert-butyl-4-hydroxy-benzyl)sulfide,isooctyl-3,5di-tert-butyl-4-hydroxybenzylmercaptoacetate.

1.8. Hydroxybenzylated malonates, for exampledioctadecyl-2,2-bis-(3,5-di-tert-butyl-2-hydroxybenzyl)-malonate,di-octadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)-malonate,di-dodecylmercaptoethyl-2,2-bis-(3,5-di-tert-butyl-4-hydroxybenzyl)malonate,bis4-(1,1,3,3-tetramethylbutyl)phenyl!-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate.

1.9. Aromatic hydroxybenzyl compounds, for example1,3,5-tris-(3,5-di-tert-butyl-4-hydroxy-benzyl)-2,4,6-trimethylbenzene,1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetra-methylbenzene,2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.

1.10. Triazine Compounds, for example2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine,2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine,2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine,2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine,1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-isocyanurate,2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine,1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexahydro-1,3,5-triazine,1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate.

1.11. Benzylphosphonates, for exampledimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate,diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate,dioctadecyl3,5-di-tert-butyl-4-hydroxybenzylphosphonate,dioctadecyl-5-tert-butyl-4-hydroxy3-methylbenzylphosphonate, the calciumsalt of the monoethyl ester of3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.

1.12. Acylaminophenols, for example 4-hydroxylauranilide,4-hydroxystearanilide, octylN-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.

1.13. Esters of β-(3.5-di-tert-butyl-4-hydroxyphenyl)propionic acid withmono- or polyhydric alcohols, e.g. with methanol, ethanol, n-octanol,i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thiaundecanol,3-thiapentadecanol, trimethylhexanediol, trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo 2.2.2!octane.

1.14. Esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acidwith mono- or polyhydric alcohols, e.g. with methanol, ethanol,n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol,ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethyleneglycol, diethylene glycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl) isocyanurate, N,N'-bis(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo2.2.2!octane.

1.15. Esters of β-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid withmono- or polyhydric alcohols, e.g. with methanol, ethanol, octanol,octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo2.2.2!octane.

1.16. Esters of 3.5-di-tert-butyl-4-hydroxyphenyl acetic acid with mono-or polyhydric alcohols, e.g. with methanol, ethanol, octanol,octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)-oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane, 4-hydroxymethyl-1 -phospha-2,6,7-trioxabicyclo2.2.2!octane.

1.17. Amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid e.g.N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamine,N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trimethylenediamine,N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hydrazine.

1.18. Ascorbic acid (vitamin C)

1.19. Aminic antioxidants, for exampleN,N'-di-isopropyl-p-phenylenediamine,N,N'-di-sec-butyl-p-phenylenediamine,N,N'-bis(1,4-dimethylpentyl)-p-phenylenediamine,N,N'-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine,N,N'-bis(1-methylheptyl)-p-phenylenediamine,N,N'-dicyclohexyl-p-phenylenediamine, N, N'-diphenyl-p-phenylenediamine,N, N'-bis(2-naphthyl)-p-phenylenediamine,N-isopropyl-N'-phenyl-p-phenylenediamine,N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine,N-(1-methylheptyl)-N'-phenyl-p-phenylenediamine,N-cyclohexyl-N'-phenyl-p-phenylenediamine,4-(p-toluenesulfamoyl)diphenylamine,N,N'-dimethyl-N,N'-di-sec-butyl-p-phenylenediamine, diphenylamine,N-allyldiphenylamine, 4-isopropoxy-diphenylamine,N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine,N-phe-nyl-2-naphthylamine, octylated diphenylamine, for examplep,p'-di-tert-octyldiphenylamine, 4-n-butylaminophenol,4-butyrylaminophenol, 4-nonanoylamino-phenol, 4-dodecanoylaminophenol,4-octadecanoylaminophenol, bis(4-methoxyphenyl)amine,2,6-di-tert-butyl-4-dimethylaminomethylphenol,2,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane,N,N,N',N'-tetramethyl-4,4'-diaminodiphenylmethane, 1,2-bis(2-methylphenyl)amino!ethane, 1,2-bis(phenylamino)propane,(o-tolyl)biguanide, Bis 4-(1 ',3'-dimethylbutyl)phenyl!amine,tert-octylated N-phenyl-1-naphthylamine, a mixture of mono- anddialkylated tert-butyl/tert-octyldiphenylamines, a mixture of mono- anddialkylated nonyldiphenylamines, a mixture of mono- and dialkylateddodecyldiphenylamines, a mixture of mono- and dialkylatedisopropyl/isohexyldiphenylamines, a mixture of mono- und dialkylatedtert-butyldiphenylamines, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine,phenothiazine, a mixture of mono- und dialkylatedtert-butyl/tert-octylphenothiazines, a mixture of mono- und dialkylatedtert-octyl-phe-nothiazines, N-allylphenothiazin,N,N,N',N'-tetraphenyl-1,4-diaminobut-2-ene,N,N-bis-(2,2,6,6-tetramethyl-piperid-4-yl-hexamethylenediamine,bis(2,2,6,6-tetramethylpiperid-4-yl)sebacate,2,2,6,6-tetramethylpiperidin-4-one, 2,2,6,6-tetramethylpiperidin-4-ol.

2. UV absorbers and light stabilisers

2.1. 2-(2'-Hydroxyphenyl)benzotriazoles, for example2-(2'-hydroxy-5'-methylphenyl)-benzo-triazole,2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)benzotriazole,2-(5'-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-(1 ,1,3,3-tetramethylbutyl)phenyl) benzotriazole,2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-chloro-benzotriazole,2-(3'-tert-butyl- 2'-hydroxy-5'-methyl-phenyl)-5-chloro-benzotriazole,2-(3'-sec-butyl-5'-tert-butyl-2'-hydroxyphenyl)benzotriazole,2-(2'-hydroxy-4'-octyloxyphenyl)benzotriazole,2-(3',5'-di-tert-amyl-2'-hydroxyphenyl)benzotriazole,2-(3',5'-bis-(α,α-dimethylbenzyl)-2'-hydroxyphenyl)benzotriazole,mixture of2-(3'-tert-butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl)phenyl)-5-chloro-benzotriazole,2-(3'-tert-butyl-5'-2-(2-ethylhexyloxy)-carbonylethyl!-2'-hydroxyphenyl)-5-chloro-benzotriazole,2-(3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)-5-chloro-benzotriazole,2-(3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)benzotriazole,2-(3'-tert-butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl)phenyl)benzotriazole,2-(3'-tert-butyl-5'-2-(2-ethylhexyloxy)carbonylethyl!-2'-hydroxyphenyl)benzotriazole,2-(3'-dodecyl-2'-hydroxy-5'-methylphenyl)benzotriazole, and2-(3'-tert-butyl-2'-hydroxy-5'-(2-isooctyloxycarbonylethyl)phenylbenzotriazole,2,2'-methylene-bis4-(1,1,3,3-tetramethylbutyl)-6-benzotriazole-2-ylphenol!; thetransesterification product of 2-3'-tert-butyl-5'-(2-methoxycarbonylethyl)-2'-hydroxyphenyl!-2H-benzotriazolewith polyethylene glycol300;, whereR=3'-tert-butyl-4'-hydroxy-5'-2H-benzotriazol-2-ylphenyl.

2.2. 2-Hydroxybenzophenones, for example the 4-hydroxy, 4-methoxy,4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2',4'-trihydroxyand 2'-hydroxy-4,4'-dimethoxy derivatives.

2.3. Esters of substituted and unsubstituted benzoic acids, as forexample 4-tertbutyl-phenyl salicylate, phenyl salicylate, octylphenylsalicylate, dibeanzoyl resorcinol, bis(4-tert-butylbenzoyl) resorcinol,benzoyl resorcinol, 2,4-di-tertbutylphenyl3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl3,5-di-tert-butyl-4-hydroxybenzoate, 2-methyl-4,6-di-tert-butylphenyl3,5-di-tert-butyl-4-hydroxybenzoate.

2.4. Acrylates, for example ethyl α-cyano-β,β-diphenylacrylate, isooctylα-cyano-β,β-diphenylacrylate, methyl α-carbomethoxycinnamate, methylα-cyano-β-methyl-p-methoxy-cinnamate, butylα-cyano-β-methyl-p-methoxy-cinnamate, methylα-carbomethoxy-p-methoxycinnamate andN-(β-carbomethoxy-β-cyanovinyl)-2-methylindoline.

2.5. Nickel compounds, for example nickel complexes of 2,2'-thio-bis-4-(1 ,1,3,3-tetra-methylbutyl)phenol!, such as the 1:1 or 1:2 complex,with or without additional ligands such as n-butylamine, triethanolamineor N-cyclohexyldiethanolamine, nickel dibutyldithiocarbamate, nickelsalts of the monoalkyl esters, e.g. the methyl or ethyl ester, of4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid, nickel complexes ofketoximes, e.g. of 2-hydroxy-4-methylphenyl undecylketoxime, nickelcomplexes of 1 -phenyl-4-lauroyl-5-hydroxypyrazole, with or withoutadditional ligands.

2.6. Sterically hindered amines, for examplebis(2,2,6,6-tetramethyl-4-piperidyl)sebacate,bis(2,2,6,6-tetramethyl-4-piperidyl)succinate,bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate,bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate,bis(1,2,2,6,6-pentamethyl-4-piperidyl)n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensate of1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinicacid, the condensate ofN,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-tert-octylamino-2,6-dichloro-1,3,5-triazine,tris(2,2,6,6-tetramethyl-4-piperidyl)nitrilotriacetate,tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butane-tetracarboxylate,1,1'-(1,2-ethanediyl)bis(3,3,5,5-tetramethylpiperazinone),4-benzoyl-2,2,6,6-tetramethylpiperidine,4-stearyloxy-2,2,6,6-tetramethylpiperidine,bis(1,2,2,6,6-pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl)malonate,3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro 4.5!decan-2,4-dion,bis(1 -octyloxy-2,2,6,6-tetramethylpiperidyl)sebacate, bis(1-octyloxy-2,2,6,6-tetramethyl-piperidyl)succinate, the condensate ofN,N'-bis-(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-morpholino-2,6-dichloro-1,3,5-triazine, the condensate of2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triazine and 1,2-bis(3-aminopropylamino)ethane, the condensateof2-chloro-4,6-di-(4-n-butylamino-1,2,2,6,6-pentamethyl-piperidyl)-1,3,5-triazineand 1,2-bis-(3-aminopropylamino)ethane,8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro4.5!decane-2,4-dione,3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)pyrrolidin-2,5-dione,3-dodecyl- 1-(1, 2,2,6,6-pentamethyl-4-piperidyl)pyrrolidine-2,5-dione,a mixture of 4-hexadecyloxy- and4-stearyloxy-2,2,6,6-tetramethylpiperidine, a condensation product ofN,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, a condensation product of1,2-bis(3-amino-propylamino)ethane and 2,4,6-trichloro-1,3,5-triazine aswell as 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No.136504-96-6!); N-(2,2,6,6-tetramethyl-4-piperidyl)-n-dodecylsuccinimid,N-(1,2,2,6,6-pentamethyl-4-piperidyl)-n-dodecylsuccinimid,2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro 4,5!decane, areaction product of 7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro 4,5!decane und epichlorohydrin.

2.7. Oxamides, for example 4,4'-dioctyloxyoxanilide,2,2'-diethoxyoxanilide, 2,2'-dioctyloxy-5,5'-di-tert-butoxanilide,2,2'-didodecyloxy-5,5'-di-tert-butoxanilide, 2-ethoxy-2'-ethyloxanilide,N,N'-bis(3-dimethylaminopropyl)oxamide,2-ethoxy-5-tert-butyl-2'-ethoxanilide and its mixture with2-ethoxy-2'-ethyl-5,4'-di-tert-butoxanilide and mixtures of ortho- andpara-methoxy-disubstituted oxanilides and mixtures of o- andp-ethoxy-disubstituted oxanilides.

2.8. 2-(2-Hydroxyphenyl)-1,3,5-triazines, for example2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine,2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-2-hydroxy-4-(2-hydroxy-3-butyloxy-propoxy)phenyl!-4,6-bis(2,4-dimethyl)-1,3,5-triazine,2-2-hydroxy-4-(2-hydroxy-3-octyloxy-propyloxy)phenyl!-4,6-bis(2,4-dimethyl)-1,3,5-triazine,2-4-(dodecyloxy/tridecyloxy-2-hydroxypropoxy)-2-hydroxy-phenyl!-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-2-hydroxy-4-(2-hydroxy-3-dodecyloxy-propoxy)phenyl!-4,6-bis(2,4-di-methylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-1,3,5-triazine,2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine, 2,4,6-tris2-hydroxy-4-(3-butoxy-2-hydroxy-propoxy)phenyl!-1,3,5-triazine,2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl-1,3,5-triazine.

3. Metal deactivators, for example N,N'-diphenyloxamide,N-salicylal-N'-salicyloyl hydrazine, N, N'-bis(salicyloyl) hydrazine, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine,3-salicyloylamino-1,2,4-triazole, bis(benzylidene)oxalyl dihydrazide,oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide,N,N'-diacetyladipoyl dihydrazide, N,N'-bis(salicyloyl)oxalyldihydrazide, N,N'-bis(salicyloyl)thiopropionyl dihydrazide.

4. Phosphites and phosphonites, for example triphenyl phosphite,diphenyl alkyl phosphites, phenyl dialkyl phosphites, tris(nonylphenyl)phosphite, trilauryl phosphite, trioctadecyl phosphite, distearylpentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite,diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite,bis(2,6-di-tert-butyl-4-methylphenyl)-pentaerythritol diphosphite,diisodecyloxypentaerythritol diphosphite,bis(2,4-di-tert-butyl-6-methylphenyl)pentaerythritol diphosphite,bis(2,4,6-tris(tert-butylphenyl)pentaerythritol diphosphite, tristearylsorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl)4,4'-biphenylene diphosphonite, 6-isooctyloxy-2,4,8,10-tetra-tert-butyl-1 2H-dibenz d,g!- 1,3,2-dioxaphosphocin,6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenzd,g!-1,3,2-dioxaphosphocin,bis(2,4-di-tert-butyl-6-methylphenyl)methylphosphite,bis(2,4-di-tert-butyl-6-methylphenyl)ethylphosphite.

5. Hydroxylamines, for example, N,N-dibenzylhydroxylamine,N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine,N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine,N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine,N-hexadecyl-N-octadecyl-hydroxylamine,N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine derivedfrom hydrogenated tallow amine.

6. Nitrones, for example, N-benzyl-alpha-phenyl-nitrone,N-ethyl-alpha-methyl-nitrone, N-octyl-alpha-heptyl-nitrone,N-lauryl-alpha-undecyl-nitrone, N-tetradecyl-alpha-tridecyl-nitrone,N-hexadecyl-alpha-pentadecyl-nitrone,N-octadecyl-alpha-heptadecyl-nitrone,N-hexadecyl-alpha-heptadecyl-nitrone,N-ocatadecyl-alpha-pentadecyl-nitrone,N-heptadecyl-alpha-heptadecyl-nitrone,N-octadecyl-alpha-hexadecyl-nitrone, nitrone derived fromN,N-dialkyl-hydroxylamine derived from hydrogenated tallow amine.

7. Thiosynergists, for example, dilauryl thiodipropionate or distearylthiodipropionate.

8. Peroxide scavengers, for example esters of β-thiodipropionic acid,for example the lauryl, stearyl, myristyl or tridecyl esters,mercaptobenzimidazole or the zinc salt of 2-mercaptobenzimidazole, zincdibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritoltetrakis(β-dodecylmercapto)propionate.

9. Polyamide stabilisers, for example, copper salts in combination withiodides and/or phosphorus compounds and salts of divalent manganese.

10. Basic co-stabilisers, for example, melamine, polyvinylpyrrolidone,dicyandiamide, triallyl cyanurate, urea derivatives, hydrazinederivatives, amines, polyamides, polyurethanes, alkali metal salts andalkaline earth metal salts of higher fatty acids for example calciumstearate, zinc stearate, magnesium behenate, magnesium stearate, sodiumricinoleate and potassium palmitate, antimony pyrocatecholate or tinpyrocatecholate.

11. Nucleating agents, for example, inorganic substances such as talcum,metal oxides such as titanium dioxide or magnesium oxide, phosphates,carbonates or sulfates of, preferably, alkaline earth metals; organiccompounds such as mono- or polycarboxylic acids and the salts thereof,e.g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodiumsuccinate or sodium benzoate; polymeric compounds such as ioniccopolymers ("ionomers").

12. Fillers and reinforcing agents, for example, calcium carbonate,silicates, glass fibres, glass bulbs, asbestos, talc, kaolin, mica,barium sulfate, metal oxides and hydroxides, carbon black, graphite,wood flour and flours or fibers of other natural products, syntheticfibers.

13. Other additives, for example, plasticisers, lubricants, emulsifiers,pigments, rheology additives, catalysts, flow-control agents, opticalbrighteners, flameproofing agents, antistatic agents and blowing agents.

14. Benzofuranones and indolinones, for example those disclosed in U.S.Pat. No. 4,325,863, U.S. Pat. No. 4,338,244, U.S. Pat. No. 5,175,312,U.S. Pat. No. 5,216,052, U.S. Pat. No. 5,252,643, DE-A-4316611,DE-A-4316622, DE-A-4316876, EP-A-0589839 or EP-A-0591102 or 3-4-(2-acetoxyethoxy)phenyl!-5,7-di-tert-butyl-benzofuran-2-one,5,7-di-tert-butyl-3- 4-(2-stearoyloxyethoxy)phenyl!benzofuran-2-one,3,3'-bis 5,7-di-tert-butyl-3-(4-2-hydroxyethoxy!phenyl)benzofuran-2-one!,5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-one,3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one,3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di-tert-butyl-benzofuran-2-one.

The weight ratio of the compounds of the formula (I) to the conventionaladditives may be 1:0.5 to 1:5.

The compounds of the formula (I) can also be used as stabilizers,especially as light stabilizers, for almost all materials known in theart of photographic reproduction and other reproduction techniques ase.g. described in Research Disclosure 1990, 31429 (pages 474 to 480).

The compounds of the formula (I) are particularly useful for stabilizingpolypropylene tapes and fibres. The invention is illustrated in moredetail by the following Examples. All percentages are by weight, unlessotherwise indicated.

Example 1

Preparation of the Compound of the Formula ##STR9##

A mixture of 35.8 g (0.2 mole) of the sodium salt of2,2,6,6-tetramethyl-4-hydroxypiperidine in 200 ml of xylene is slowlyadded to a solution of 36.9 g (0.2 mole) of cyanuric chloride in 200 mlof xylene cooled to -10° C. Subsequently, the reaction mixture isstirred for 1 hour at 0° C., heated to 60° C. and under vacuum, 250 mlof xylene are separated off.

The mixture is cooled to room temperature and 82.9 g (0.21 mole) ofN,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,6-hexanediamine in 100 ml ofxylene are added. Then, the mixture is heated to 60° C. for 2 hours andfurther 2 hours at reflux. After cooling, 20.0 g (0.5 mole) of NaOH areadded in powder form and the reaction mixture is heated 10 hours atreflux, the reaction water being separated off azeotropically.

After cooling and filtration over earth, the solution is evaporated at140° C. and 1 mbar. After cooling again, the desired product is obtainedas a white powder with a melting point of 173°-183° C. and Mn=5300g/mole.

Example 2

Preparation of the Compound of the Formula ##STR10##

A) Preparation of (4,6-dichloro-1,3,5!-triazin-2-yl)-(2,2,6,6-tetramethyl-4-piperidyl)-amine.

To a solution of 90 g (0.49 moles) of cyanuric chloride in 700 ml of1,2-dichloroethane, cooled to -10° C., a solution of 76.2 g (0.49 moles)of 2,2,6,6-tetramethyl-4-piperidylamine in 100 ml of 1,2-dichloroethaneis slowly added, maintaining the temperature at -10C. during theaddition. Then, the mixture is stirred for 1 hour at -10° C. and asolution of 21.4 g (0.54 moles) of sodium hydroxide in 60 ml of water isadded, maintaining the above mentioned temperature during the addition.

Subsequently, the mixture is stirred for 1 hour at room temperature andthe organic phase is collected. Then, the organic phase is washed twicewith 150 ml of water, dried over sodium sulfate and evaporated at 60°C./1 mbar.

After drying in an oven, a solid is obtained with a melting point of150°-152° C.

CI analysis:

Calculated: 23.31%

Found: 22.97%

B) A mixture of 60.8 g (0.2 moles) of (4,6-dichloro-1,3,5!-triazin-2-yl)-(2,2,6,6-tetramethyl-4-piperidyl)-amine and 82.9 g(0.21 moles) ofN,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,6-hexanediamine in 200 ml ofxylene is heated to reflux and stirred for 1 hour at this temperature.Then, the mixture is cooled to 60° C. and 22 g (0.55 moles) of sodiumhydroxide are added in powder form.

Subsequently, the reaction mixture is heated for 2 hours to reflux,cooled again to 60° C. and 30 ml of water are added.

Then, the mixture is heated at reflux and under stirring for 12 hours,the reaction water and the added water being separated offazeotropically.

After cooling and filtration over earth, the solution is evaporated at140° C./1 mbar.

After cooling, a white solid product with a melting point of 163°-170°C. and Mn=2190 g/mole is obtained.

Example 3

By using the same reactants and the same synthesis conditions as inExample 2, but with an excess ofN,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,6-hexanediamine (20% molarexcess), a compound of the same formula as in Example 2, with a meltingpoint of 132°-135° C. and Mn=1485 g/mole is obtained.

In the above Examples 1 to 3, the number average molecular weight isdetermined according to the following procedure:

The determination is carried out in a vapor pressure osmometer ®OSMOMAT070 (®GONOTEC-Germany). The osmometer consists of a thermostatic chambersaturated with the analytical solvent in which two thermistors aresituated; one for reference and one for measurement.

Before the beginning of the measurement a drop of pure solvent is put oneach thermistor and the bridge is adjusted to zero after 5 minutes.

Then, a solution containing a substance of known molecular weight(M_(Ref)) is measured. For this purpose the solvent on the measurementthermistor is replaced by a drop of a known concentration solution andthe change of resistance to rebalance the bridge after 5 minutes isdetermined. This procedure is carried out for four solutions ofdifferent concentrations (0.01 molal, 0.02 molal, 0.03 molal and 0.04molal*). Extrapolation to infinite dilution gives K_(Ref)=const/M_(Ref).

The measurement are repeated with the solutions containing a substanceof unknown molecular weight (Mn). Extrapolation to infinite dilutiongives K_(meas) =const/Mn.

Then, the number average molecular weight is calculated according to thefollowing equation: ##EQU1## Example 4 Light-Stabilizing Action inPolypropylene Fibres.

2.5 g of the stabilizer indicated in Table 1, 1 g oftris(2,4-di-t-butylphenyl) phosphite, 1 g of calcium monoethyl3,5-di-t-butyl-4-hydroxybenzyl-phosphonate, 1 g of calcium stearate and2.5 g of titanium dioxide are mixed in a slow mixer with 1000 g ofpolypropylene powder having a melt index=12 g/10 min (measured at 230°C. and 2.16 kg).

The mixtures are extruded at 200°-230° C. to obtain polymer granuleswhich are then converted into fibres using a pilot-type apparatus(®Leonard-Sumirago(VA), Italy) and operating under the followingconditions:

extruder temperature: 200°∝230° C.

head temperature: 255°-260° C.

stretch ratio: 1:3.5

linear density: 11 dtex per filament

The fibres prepared in this way are exposed, after mounting on whitecardboard, in a 65WR Weather-O-Meter (ASTM D2565-85) with a black paneltemperature of 63° C.

For samples taken after various times of exposure to the light, theresidual tenacity is measured using a constant-speed tensometer, and theexposure time in hours needed to halve the initial tenacity (T₅₀) isthen calculated.

For purposes of comparison, fibres prepared under the same conditions asstated above, but without adding the stabilizers of the presentinvention, are also exposed.

The results are shown in Table 1.

                  TABLE 1                                                         ______________________________________                                        Stabilizer        T.sub.50 (hours)                                            ______________________________________                                        Without stabilizer                                                                               370                                                        Compound of Example 1                                                                           3440                                                        Compound of Example 2                                                                           3440                                                        Compound of Example 3                                                                           3500                                                        ______________________________________                                    

Example 5

Light-Stabilizing Action in Polypropylene Tapes

1 g of the compound referred to in Table 2, 1.0 g oftris(2,4-di-t-butylphenyl) phosphite, 0.5 g of pentaerythritol tetrakis3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate! and 1 g of calciumstearate are mixed in a low-speed mixer with 1000 g of polypropylene inpowder form, having a melt index=12 g/10 min (measured at 230° C. and2.16 kg).

The mixtures are extruded at 200°-230° C. in order to obtain polymergranules which are then converted into stretched tapes having athickness of 50 μm and a width of 2.5 mm, using a semi-industrialapparatus (®Leonard-Sumirago (VA) Italia), operating under the followingconditions:

extruder temperature: 210° 230° C.

temperature of the head: 240° 260° C.

stretch ratio: 1:6

The tapes material thus prepared is exposed, after mounting on whitecardboard, in a Weather-O-Meter, Model 65WR (ASTM D2565-85) with a blackpanel temperature of 63° C. The residual tenacity is measured on samplestaken after exposure to light for different periods of time, using aconstant-velocity dynamometer, and the time (in hours) required toreduce the initial tenacity by 50% (T⁵⁰) calculated from these values.

For comparison purposes, tapes which have been prepared under theconditions described above but without the addition of the stabilizingagents are also exposed. The results are shown in Table 2.

                  TABLE 2                                                         ______________________________________                                        Stabilizer        T.sub.50 (hours)                                            ______________________________________                                        Without stabilizer                                                                               560                                                        Compound of Example 1                                                                           3320                                                        Compound of Example 2                                                                           3495                                                        Compound of Example 3                                                                           3300                                                        ______________________________________                                    

We claim:
 1. A compound of the formula (I) ##STR11## wherein n is anumber from 1 to 20;the radicals R₁ are independently of one anotherhydrogen, C₁ -C₈ alkyl, --O, --OH, --CH₂ CN, C₁ -C₁₈ alkoxy, C₅ -C₁₂cycloalkoxy, C₃ -C₆ alkenyl, C₇ -C₉ phenylalkyl which is unsubstitutedor substituted on the phenyl by 1, 2 or 3 C₁ -C₄ alkyl; or C₁ -C₈ acyl;R₂ has one of the meanings given for R₁ ; X is C₂ -C₄ alkylene; and Y is--O-- or >NH; with the proviso that in the individual recurrent units ofthe formula (I), each of the radicals R₁, R₂, X and Y has the same ordifferent definitions.
 2. A compound according to claim 1 wherein theradicals R₁ are independently of one another hydrogen, C₁ -C₄ alkyl,--OH, C₆ -C₁₂ alkoxy, C₅ -C₈ cycloalkoxy, allyl, benzyl or acetyl; andR₂ has one of the meanings given for R₁.
 3. A compound according toclaim 1 wherein the radicals R₁ are identical and are hydrogen, methylor cyclohexyloxy; R₂ has one of the meanings given for R₁ ; and X is C₂-C₆ alkylene; with the proviso that in the individual recurrent units ofthe formula (I), each of the radicals R₁, R₂, X and Y has the samedefinitions.
 4. A compound according to claim 3 wherein the radicals R₁are identical and are hydrogen or methyl; and R₂ has one of the meaningsgiven for R₁.
 5. A compound according to claim 1 wherein X is hexylene.6. A compound according to claim 1 wherein n is a number from 3 to 20.7. A compound according to claim 1 wherein Y is --O--.
 8. A compositioncontaining an organic material susceptible to degradation induced bylight, heat or oxidation and at least one compound of the formula (I)according to claim
 1. 9. A composition according to claim 8 wherein theorganic material is a synthetic polymer.
 10. A composition according toclaim 8 wherein the organic material is polyethylene or polypropylene.11. A method for stabilizing an organic material against degradationinduced by light, heat or oxidation which comprises incorporating intosaid organic material at least one compound of the formula (I) accordingto claim 1.